ME 216 – Engineering Materials II

Chapter 12
Heat Treatment (Part I)

Mechanical Engineering Prof. Dr. Ömer Eyercioğlu

University of Gaziantep
 Introduction
 Heat treatment is heating and cooling a metal in solid state to change its physical properties.

 According to the procedure used, metals can be hardened to resist cutting and abrasion, or can be
softened to permit further machining. Therefore, with proper heat treatment:
 internal stresses can be removed
 grain size can be reduced
 toughness can be increased
 a hard surface can be produced on a ductile interior

 Phases and microstructures in a metal can be modified, thus combination of properties most suitable
for a given application can be chosen.
 The microstructures of single-phase metals can be adjusted by:
 plastic deformation
 recrystallization
 solid solution additions
 crystal orientation
 In addition, there are additional means of control of microstructures in multi-phase metals:
 The relative amounts of the phases may be varied.
 The grain size may be varied.
 The shape and distribution of phases can be modified.
 Each of these three microstructural variations provides means of modifying the properties of metals. 1
 Basic Concepts
 On heating pure iron from room temp. to its melting
point, it undergoes allotropic modifications. On
cooling molten iron to room temp, transformations
take place in the reverse order (at approximately
the same temperatures as on heating).
 -iron is stable below 911 °C, -iron is stable
between 911 °C and 1392 °C, and -iron is stable
between 1392 °C and 1536 °C (melting point).
 Iron is ferromagnetic at room temp. Its magnetism
vanishes completely at 769 °C.
 Carbon is the most important alloying element in
steel. At room temp, the solubility of C in -iron is
almost zero. Thus, it separates from crystal structure
and forms a chemical compound with iron, which is
known as cementite. Cementite and ferrite may show
a lamellar structure, which is known as pearlite.
 When Fe is alloyed with C, the transformation will
take place within a temp. range, which is dependent
on C content as shown in Fe-C equilibrium diagram.
Solubility of carbon in austenite is much greater than
in ferrite (i.e. 2% C at 1193 °C). 2
 Time-Temperature-Transformation (TTT)
 Fe-C diagram can only describe the situation when Eutectoid Steel
equilibrium is established between Fe & C. (0.8% C)

 However, in heat treatment operation, time of heating

and cooling is also a significant factor.

Heating
 On heating eutectoid steel (0.8% C), phase diagram
Hypo-Eutectoid Steel
shows that the transformation to austenite occurs at (0.45% C)
723 °C. However, it tells us nothing about how long
this transformation will take to start and to complete.

 From heating curve, it can be predicted that when

temp. is 730 °C, transformation starts in 30 s. If steel
is heated to 750 °C transformation begins in 10 s, and
if heated to 810 °C it begins in 1 s. Hyper-Eutectoid Steel
(1.2% C)
 Transformation of pearlite to austenite & cementite is
completed in about 6 s at 810 °C. If steel is to be fully
austenitic, it must be held at this temp. for about 5 h.

 Transformations of hypo-eutectoid steel (0.45% C)

and hyper-eutectoid steel (1.2% C) are also shown.
 Time-Temperature-Transformation (TTT)
Cooling
 General appearance of a structure during cooling is dependent upon temp. and time of transformation.
 The transformation of steel at a certain temp. can be investigated by cooling from austenite to that temp,
letting the transformation take place, and then quenching to room temp.

 This is best explained by construction of Time-Temperature-Transformation (TTT) diagrams:

1. Prepare samples from the same bar.

Cross-section must be small for quick
reactions to changes in temp.
2. Place samples in a molten salt bath at
the proper austenitizing temp. They
should be held at this temp. long
enough to become purely austenite.
3. Place samples in an incubation bath,
held at a constant subcritical temp.
4. After varying duration, each sample is
quenched in cold water or iced brine.
5. After cooling, each sample is checked
for hardness and structure.
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 Time-Temperature-Transformation (TTT)
Cooling
 As a result of such experiments, two points are plotted at
subcritical temp: the times for beginning and end of Eutectoid
transformation. It is also common practice to plot the time Steel
(0.8% C)
for 50% transformation.
 Construction of a reasonably accurate diagram requires
heat treatment and metallographic study of more than one
hundred individual samples.
 TTT diagrams for different steels are shown in figures.
Hypo-Eutectoid
Steel
(0.45% C)

Hyper-Eutectoid
Steel
(1.0% C)
 Facts on TTT Diagrams
 Family of S-shaped curves at certain constant temp. are used
to construct the TTT diagrams.
 They are used for isothermal (constant temp.) transformations
(i.e. the material is cooled quickly to a given temp. before
transformation occurs, and then kept at that temp.)

 At low temp, transformation occurs sooner (controlled by rate

of nucleation) with slow grain growth (controlled by diffusion).
This leads to fine-grained microstructure with thin-layered
structure of pearlite (fine pearlite).

 At high temp, high diffusion rates allow for larger grain

growth and formation of thick-layered structure of pearlite
Complete TTT diagram for Fe-C
(coarse pearlite).
alloy of eutectoid composition
 At compositions other than eutectoid, a proeutectoid phase
(ferrite or cementite) coexists with pearlite. Additional curves
for such transformation must be included on TTT diagrams.

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 Formation of Pearlite
 Pearlite is the characteristic lamellar structure of alternate layers of ferrite () and cementite (Fe3C).
 Just below 723 °C (eutectoid temp, TE), coarse pearlite is formed with soft structure (about 15 HRC).
 As transformation temp. decreases, fine pearlite is obtained, and the whole structure becomes harder.
 Pearlite formation is initiated at austenite () grain boundaries or at some other disarray in  grains. First,
Fe3C is initiated (causing carbon depletion in adjacent regions), then transformed to  platelets.

Coarse Pearlite Fine Pearlite

(softer, formed at just below TE) (harder, formed at well below TE)

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 Formation of Bainite
 Below 550 °C, bainite starts to separate along with pearlite.

 Its formation is initiated on nuclei of , growing as platelets

from grain boundaries. The carbon content of surrounding 
increases continuously, and forms platelets of Fe3C.

 Bainite structure is not regularly lamellar as that of pearlite.

 Depending on temp. of formation, it is classified as:

 upper bainite (from hardness of about 40 HRC)
 lower bainite (to hardness of about 60 HRC)

 Such increase in hardness is resulting from decrease in

size & spacing of carbide platelets since transformation
temp. decreases.
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 Formation of Martensite
 Martensite is formed if austenitized structure is rapidly cooled
(quenched) to a relatively low temp (about room temp).
 As cooling continues, there is very little carbon migration while 
is transforming. Thus, carbon atoms remain in solid solution of
-iron. As the space available for carbon atoms is less in -iron
than -iron, carbon atoms will expand the lattice. The resulting
state of stress increases the hardness of steel.
 Martensite is a super-saturated solution of carbon in -iron.
 As seen from diagram, each temp. below martensite start (Ms)
corresponds to a definite proportion of martensite.

Martensite phase (needle-shaped grains) with austenite

(white regions that failed to transform during rapid quench)

Body-centered tetragonal unit cell

(c > a) for martensitic steel structure,
showing iron atoms (circles) and
sites occupied by carbon atoms (Xs).
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 Formation of Martensite & Retained-Austenite
 Martensite structure in steels is classified as:
 massive martensite: Steels having up to 0.6% C.
Consists of packets of parallel platelets that can
only be resolved in electron microscope.
 acicular martensite: More familiar martensite,
found only in steels having 1% C or more.

Retained-Austenite
 Most of  in steel will transform to martensite during
quenching to room temp. The untransformed portion
is retained austenite, varying with carbon content.
 If temp. is below room temp, the transformation to
martensite continues. This way of increasing amount
of martensite is called sub-zero treatment.
 In martempering process, cooling is interrupted just
above Ms, so steel is allowed to cool to room temp.
This stabilizes , causing martensite formation to start
at a lower temp, thus resulting in a higher proportion
of retained austenite at room temp.
 So, martempered (air-hardened) steel has larger
amount of retained austenite than oil-hardened one.
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 Effect of Alloying Elements on TTT Curves
 Alloying elements delay formation of  and Fe3C (i.e. curves in TTT diagram are shifted to the right).
 Start temp. for transformation of bainite (Bs) and martensite (Ms) are altered by following equations:
Bs  C   830  270  %C   90  % Mn   37  % Ni   70  %Cr   83  % Mo 
M s  C   539  423  %C   30.4  % Mn   17.7  % Ni   12.1 %Cr   7.5  % Mo 

 C, Ni, Mn, Si move pearlite and

bainite curves to right, but not
separating them appreciably on
the temp. scale.
 Mo, Cr, V move pearlite curve
markedly toward right and also
displace it upwards to higher
temp. However, bainite curve is
not moved much toward right,
but depressed to lower temp.

TTT diagram for unalloyed TTT diagram for an alloy steel

eutectoid steel (0.8% C) (type 4340: Ni-Cr-Mo with 0.4% C)
 Continuous Cooling Transformation (CCT)
 TTT curves refer to transformation at a cst temp, but most heat treatment operations involve continuous
cooling. From TTT diagrams, Continuous Cooling Transformation (CCT) diagrams are derived to
show transformations under continuous cooling.

 Figure shows CCT curves, superimposed on

TTT diagram of an eutectoid steel.

 Curve 1 indicates a very slow cooling rate

(typical of annealing), allowing transformation
to coarse pearlite. Transformation starts at
X1 and completed at X1' after which material
may be cooled without any change.

 Curve 2 illustrates an isothermal annealing,

which results in more uniform microstructure.

 Curve 3 refers to cooling rate of normalizing:

transformation starts at X3 and completed at
X3'. Time difference between these points is
shorter than that in Curve 1 (i.e. btw X1 and
X1'), and hence the structure will show more
variation in the fineness of pearlite.
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 Continuous Cooling Transformation (CCT)
 Curve 4 is slow oil quenching, which results
in fine pearlite.

 Curve 5 is fast oil quenching: transformation

to fine pearlite starts at X5 and stops at X5'.
Below this temp, no transformation occurs
until X5" on the martensite start line (Ms).
Thereby, remaining austenite transforms to
martensite, and hence final microstructure is
25% fine pearlite and 75% martensite.

 Curve 6 represents fast water quenching,

which avoids nose of pearlite transformation.
It remains austenitic until the martensite start
line (Ms) is reached at X6'. Transformation to
martensite occurs between lines of start (Ms)
and finish (Mf). The final microstructure will
be entirely martensite of high hardness.

 Curve 7 is called Critical Cooling Rate (tangent to top pearlite nose region, which does not transform to
pearlite). Any cooling rate slower than critical rate will enter pearlite region, so complete martensitic
transformation will not occur. Any cooling rate faster than critical rate will form only martensite.
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 An Example on using TTT diagrams
 On the given isothermal transformation diagram
for Fe-C alloy with 0.45% C, sketch time-temp.
paths to produce the following microstructures:

a) 42% proeutectoid ferrite & 58% coarse pearlite

 First, produce ferrite
 Then, produce pearlite (closer to TE)

b) 50% fine pearlite & 50% bainite

 First, produce pearlite (on the line of P-B)
 Then, produce bainite (middle of B region)
(c)

c) 50% martensite & 50% austenite

 Cool until middle of M region (btw Ms & Mf) (d) (b) (a)

d) 100% martensite
 Quenching (rapid cooling) until room temp.

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